Durable-to-washing finish for the inhibition of gas fading of spandex fibers and fabrics



United States Patent ABSTRACT OF THE DISCLOSURE An aqueous textilefinish composition, particularly adapted for the prevention of gasfading or yellowing on age of spandex blend fabrics comprising from 0.1to 10 parts by weight of a hydrolyzed vinyl ether-maleic anhydridecopolymer, from 1 to 20 parts by weight of a thermosetting melamine typeresin, from 0.2 to parts by weight of an acidic catalyst, from 0 toparts by weight of an acrylic latex, from O to 0.5 parts by weight ofammonium zirconyl carbonate, from 0 to 10 parts by weight of fabricsoftener selected from the group consisting of anionic and nonionicfabric softeners, and the remainder water.

The present invention relates to novel textile finish compositions;textile materials treated with said finish compositions and the methodfor treating the textile materials.

Many textiles are commonly impregnated with some material which impartsa desirable finish thereto. However, the problem of gas fading, wherebythe textiles, for example, spandex blend fabrics, are discolored hascontinued to remain among the leading problems in the textile field. Gasfading of the textile is caused by nitrogen and sulfur oxides in theatmosphere. For example, under the influence of gas fumes, such as gasdryers, smog atmosphere, furnace or stove gases, the textile fiber turnsprogressively yellower.

In'order to overcome this problem, it has been proposed to use ahydrolyzed vinyl ether-maleic anhydride copolymer. While the use of ahydrolyzed vinyl ethermaleic anhydride copolymer with or withoutsofteners, as a textile finishing agent contributed substantially tofinished textiles, said finished textiles continued to have the seriousfailing of gas fading, since the hydrolyzed vinyl ether-maleic anhydridecopolymer is easily removed by one or two home launderings leaving thetextile susceptible to gas fading.

I have now discovered novel and unobvious textile finish compositionswhich may be used as gas fading inhibitors and which, when applied totextile materials will afford the finished textile materials withexcellent protection to gas fading even after repeated washings.

It is among the objects of this invention to provide novel gas fadinginhibiting textile finish compositions which comprise (1) athermosetting methylolated melamine type resin such as a cross-linkable,thermosetting hydroxylated, alkylated, or hydroxyalkylated methylolatedmelamine resin; (2) a hydrolyzed vinyl ether-maleic anhydride copolymer,especially poly (vinyl-methyl ethermaleic anhydride), such as GantrezAN-119 (r Sp. 0.1- 0.5), Gantrez AN-139 (1 Sp. 1.01.4), Gantrez AN-l49(1; Sp. 1.5-2.0), Gantrez AN-l69 (1; Sp. 2.6-3.5), and the like; (3) anacidic catalyst, such as 2-amino-2-methyl- 1 propanol hydrochloride, 2amino-methyl-l propanol phosphate, monoethanolamine hydrochloride,Z-amino-lbutanol phosphate, triethanolamine phosphate, diethanolaminehydrochloride, 1-amino-2-methyl-2-butanol phosphate, l-amino 2 methyl2-butanol hydrochloride, 3-

amino-Z-methyl 2 butanol hydrochloride, diammonium phosphate, ammoniumchloride, magnesium chloride, zinc chloride, oxalic acid, citric acid,zinc nitrate and the like and (4) the remainder water. Said noveltextile finish compositions may also contain, if desired, one or moreother ingredients like acrylic latices, such as methyl, ethyl, propyl,etc., esters of acrylic or methacrylic acids or amides, and the likesuch as Rhoplex HA-8, Rhoplex K-3, Rhoplex HA-l2, Rhoplex HA-l6, RhoplexHA-20, Rhoplex E-32, each of these with or without oxalic acid as arapid curing catalyst, Polectron 130, and other emulsion copolymersfamiliar to those in the textile trade as finishing agents, whichfunction partially as binders and partially as fabric hand modifiers;ammonium zirconyl carbonate, which functions as an auxiliary binder anda wide variety of anionic or nonionic fabric softeners such as salts ofcarboxylated, sulfonated or sulfated compounds containing a long alkylchain, polyoxyethylenated long chain active hydrogen compounds, fattyacid esters of mono, di, and polyhydride alcohols, long chain fatty acidamides, and the like, such as Emulphor VT-510, Soromine MG-lOO, SoromineN-SO, Soromine AL, Soromine AN-25, Blandofen SL, Avitex K, Ahcovel NC,Nopcotex 668, Profine Paste and Soromine AT.

The cross-linkable, thermosetting hydroxylated and hydroxy methylatedmelamine resins used in this invention may be the hydroxylated andhydroxyalkylated products produced by treating aminotriazines withformaldehyde or urea followed by treatment With a lower aliphaticalcohol as shown by U.S. Pat. 2,454,078, for example. Among thepreferred resins used in this invention that may be mentioned are thecross-linkable thermosetting hydroxymethylated melamine resins, such asAmerican Cyanamides Aerotex Resin M-3 and Aerotex Resin 23 Special andMonsantos Resloom M80.

Another object of this invention is to provide textile materials, suchas glass fibers; celulose fabrics or fibers, i.e., cotton and rayon;polyester fabrics or fibers; polyamide fabrics or fibers, i.e., nylon;and particularly spandex (segmented polyurethane) blend fabrics,especially spandex blends which have been treated with the abovementioned novel textile finish compositions and the method of saidtreatment. Other objects of this invention will become more apparent asthe disclosure proceeds.

The quantitative proportions in which the components are used incarrying out the invention may vary Within wide limits for the amountspresent depend upon such conditions as the particular fabric or fiberbeing treated, the desired commercial finish, and the like. For example,the hydrolyzed vinly ether-maleic anhydride copolymer may be present inthe range of about 0.2 to about 5.0 parts by weight; the thermosettingmelamine type resin may be present in the range of about 1 to about 20parts by weight; the acidic catalyst may be present in the range ofabout 0.2 to about 5.0 parts by weight; the optional ingredients such asthe acrylic latices may be present in the range of 0 to about 8 parts byWeight; ammonium zirconyl carbonate may be present in the range of 0 toabout 05 part by weight; and the softeners may be pres ent in the rangeof 0 to about 10 parts by weight. However, it has been found thatexceptionally good finishes have been obtained when the hydrolyzed vinylethermaleic anhydride copolymer is present in the range of about 1.5 toabout 3 parts by weight; the thermosetting resin is present in the rangeof about 2.5 to about 8 parts by weight; the acidic catalyst is presentin the range of about 0.5 to about 1.4 parts by weight, the acryliclatices is present in the range of 0 to about 3.0 parts by weight; theammonium zirconyl carbonate is present in the range of 0 to about 0.5part by weight and the softeners are present in the range of O to about3 parts by weight.

These novel textile impregnating compositions may be applied to textilesin the form of a solution, emulsion, or dispersion in water or someother inert liquid. It will be apparent that the solution employed forimpregnating the fabric must not be too concentrated for viscous or anuneven finish may be obtained. On the other hand, the solution employedfor impregnating the fabric must contain a suificient amount of theimpregnating composition so that the fabric will pick up and retain asufficient amount thereof to impart the desired finish thereto. Theamount of impregnating composition which should be incorporated in thesolution employed to impregnate the fabric in order that a suificientamount will be retained by the fabric to impart the desired finishthereto can readily be determined by simple preliminary experiments.

The instant novel textile finish compositions may be applied by anyknown conventional method such as by padding or the heated jig method,the preferred procedure being the padding operation.

The following examples are illustrative of the present invention and arenot to be regarded as limitative. It is to be understood that all parts,percentages and proportions referred to herein and in the appendedclaims are by weight unless otherwise indicated.

EXAMPLE I A textile finish composition was prepared containing thefollowing:

Percent Gantrez AN139, hydrolyzed 2.0 Aerolex Resin M-3 (across-linkable thermosetting hydroxymethylated melamine resin) 5.0Catalyst X-4 (a zinc nitrate solution of Sun Chemical) 1.4 EmulphorVT-5l0 (a fatty acid ethoxylate softener) 1.0 Ammonium zirconylcarbonate solution 0.3

Water 90.3

A large piece of 30/70 bare Lycra/ nylon knitted fabric was padded withthe above composition at about 60% wet pickup, air dried and cured forthree minutes at 270275 F.

A portion of the treated fabric was then washed a series of six times at120 F. in Tide solution, rinsed and dried. The washed and unwashedtreated samples Were then exposed to one cycle of gas fading by thestandard test described in AATCC STM-231962. The unwashed treated sampleshowed excellent resistance to gas fading while the treated sample whichhad been Washed six times exhibited only slightly more fading than theunwashed sample.

EXAMPLE II By way of comparison, Example I was repeated using an aqueoussolution of 1.5% Gantrez AN-139 alone.

A textile finish composition was prepared containing the following:

Percent Gantrez AN139, hydrolyzed 1.5 Water 98.5

A large piece of 30/70 bare Lycra/nylon knitted fabric was padded withthe above composition at about 60% wet pickup, air dried and cured forthree minutes at 270-275 F.

A portion of the treated fabric was then washed 2. series of six timesat 120 F. in Tide solution, rinsed and dried. The washed and unwashedtreated samples Were then exposed to one cycle of gas fading by thestandard test described in AATCC STM-23-1962. The unwashed treatedsample showed excellent resistance to gas fading while the treatedsample which had been washed six times exhibited pronounced yellowingafter only one wash cycle and showed progressively more yellowing afterthe second and through the sixth washes.

4 EXAMPLE III Various pieces of 30/ 70 bare Lycra/ nylon knitted fabricwere padded at about 60% wet pickup with the following textile finishcompositions, air dried and cured for three minutes at 270 F. Portionsof the various treated fabrics were washed three to six times at 120 F.in Tide solution, rinsed and dried. These portions of the treated andwashed fabrics were then exposed to one cycle of gas fading by thestandard test described in AATCC STM-23-1962.

In all cases the samples treated with the instant novel textile finishcompositions showed much superior gas fading inhibition properties thana control sample treated with Gantrez AN-139 alone.

Composition A Percent Gantrez AN-139 3.0 Resloom M (cross-linkablethermosetting hydroxymethylated melamine resin) 2.5 Ammonium chloride0.5 Rhoplex HA-8 (acrylic latex-hand modifier) 2.0 Water 92.0

Composition B Gantrez AN-139 1.5 Aerotex Resin 23 Special(cross-linkable thermosetting hydroxymethylated melamine resin) 8.0Catalyst AC (an organic hydroxyamine hydrochloride acidic catalyst) 1.0Water 89.5

Composition C Percent Gantrez AN-139 1.5 Aerotex Resin M-3 5.0 Zincnitrate 0.5 Water 93.0

Composition D Gantrez AN139 1.5 Aerotex Resin M-3 5.0 Catalyst AC 0.8Water 92.7

Composition E Gantrez AN-139 1.5 Aerotex Resin M-3 5.0 Catalyst AC 0.8Ammonium zirconyl carbonate solution 0.3 Water 92.4

Composition F Gantrez AN-139 1.5 Aerotex Resin M-3 5.0 Zinc nitrate 0.5Ammonium zirconyl carbonate solution 0.3 Water 92.7

Composition G Gantrez AN-139 3.0 Aerotex Resin M3 5.0 Zinc nitrate 0.5Emulphor VT-S 10 2.0 Water 89.5

Composition H Gantrez AN-139 3.0 Aerotex Resin M-3 5.0 Catalyst AC 0.8Emulphor VT-510 2.0 Water 89.2

Composition I Gantrez AN-l39 3.0 Aerotex Resin M-3 5.0 Zinc nitrate 0.5Rhoplex HA-12 (acrylic latex hand modifier)--- 3.0 Oxalic acid 0.1Emulphor VT-5 1.0 Water 87.4

Composition I Gantrez AN139 2.0 Aerotex Resin M-3 5.0 Catalyst AC 1.4Ammonium zirconyl carbonate solution 0.3 Emulphor VT-S 10 1.0 Water 90.3

Like results were also obtained when the Lycra fabric is cured with thiscomposition for two minutes and 10 seconds at 300 F. or 55 seconds at330 F.

Various modifications and variations of this invention will be obviousto a worker skilled in the art and it is understood that suchmodifications and variations are to be included within the purview ofthis application and the spirit and scope of the appended claims.

I claim:

1. A segmented polyurethane blend textile material impregnated with anaqueous textile finish composition consisting essentially of from 0.1 to10 parts by weight of a hydrolyzed methyl vinyl ether-maleic anhydridecopolyrner, from 1 to 20 parts by weight of a thermosetting methylolatedmelamine type flexible finishing resin selected from the groupconsisting of hydroxylated, alkylated and hydroxyalkylated melamine typeresins, from 0.2 to 5 parts by weight of an acidic catalyst, from 0 to10 parts by weight of an acrylic latex, selected from the groupconsisting of acrylic latices based upon esters and amides of acrylicand methacrylic acids, from 0 to 0.5 parts by weight of ammoniumzirconyl carbonate, from 0 to 10 parts by weight of fabric softenerselected from the group consisting of anionic and nonionic fabricsofteners, and the remainder water.

2. The spandex blend textile material of claim 1 wherein said materialhas been heat cured.

References Cited UNITED STATES PATENTS 3,355,314 11/1967 Gagnoni et a1.260-29.4

3,235,443 2/ 1966 Greenman et al 260-29.4

3,334,072 8/ 1967 Sellet 26029.4

3,335,314 11/1967 Gagnoni et al. 260-29.4

MURRAY TILLMAN, Primary Examiner JOHN C. BLEUTGE, Assistant Examiner US.Cl. X.R.

